Process of producing phthalocyanine compounds



Patented July 19, 1938 UNITED "STATES 2,124,419. PROCESS OF" PRODUCING PI-ITHALOCYA NINE COMPOUNDS Isidor' Morris Heilbron, Manchester, England, Francis Irving, Grangemouth, Scotland, and Reginald Patrick Linstead, London, England,

assignors to Imperial Chemical Industries Limited, a corporationjof Great Britain No Drawing. Application May 14, 1936, Serial No. 79,815. In- Great Britain November 16,

1932 5 Claims.

This application relates to the manufacture of coloring matters of the phthalocyanine series, and constitutes a continuatiomin-part of our copending application, Serial No. 698,216,. filed 5 November 15, 1933. I

It is an object of this invention to provide an improved process for the manufacture of coloring matters of the phthalocyanineseries, especially those containing combined metal of the group consisting of iron, nickel, and cobalt. Other and further important objects of this invention will appear as the description proceeds.

In British Patent Specification No. 322,169 there is described a process for the production of blue to green coloring matters by heating phthalic anhydride with ammonia and certain metals or metal compounds including iron, cuprous' chloride and nickel sulphide; In British 0 Patent Specification No. 389,842, (corresponding to U. S. Patent No. 2,000,051). there is described a process for the production. of nitrogen-containing coloring matters of complex constitution which comprises heating an o-cyanoarylcarboxyamide in the presence of specified'metalsand metal. compounds, amongthem iron, nickel, co-

balt and their oxides or sulfides; Thesecoloringmattersare described as'purple to green in color and stated to appear to belong to. one general class, this class appearing to include the said coloring matters of British Patent Specification No. 322,169.

We have. now found that coloring matters of the same general series containing in chemical combination a metal of. the magnetic series, 33 namely iron, nickelor cobalt, may be obtained more readily and. efliciently by: heating the corresponding metal or a compound thereof with an o-arylene-dicyanide, such as phthalonitrile.

V The'heating maybe effected immediately be- 40 tween the o-arylene-dicyanide and the metal or metal compound, such as the chloride; oxide or sulphide, or it may be carried out in the presence of a suitable solvent or diluent. A high boiling inert organic solvent, such as naphthalene, methylnaphthalene or chloronaphthalene,

particularly suitablev for this;purpose. Tertiary bases such as quinoline, pyridine or dimethylaniline may also be employed. a

The temperature of the reaction will depend 50 on the boiling point or fusing point of the mixture employed or on the constituents of the mixture and it will generally be within the range of 150 to 400 C.

The reaction is applicable to substituted phthalonitriles, such as methyl-, halogenor niremoved by extraction with water, if it iswater soluble, or by precipitating the pigment from concentrated sulfuric acid. The'coloring matters may also be purified by crystallization from a suitable solvent, e. g. quinoline or chloronaph thalene, or by sublimation.

Working according to this new process the coloring matters are, generally speaking, formed with greater readiness than according to those of the above-mentioned specifications and higher yields; in some cases nearly the theoretical, are

obtained. Purification may be effected as already I described in the said specification.

The coloring matters may be employed as pigments. For instance they may be made into lakes with the usual substrata. Such lakes may be used as coloring matters for varnishes and inks.

The following examples-in which parts are by weight illustrate but do not limit the invention. Example 1 I I 6.5 parts of phthalonitrile and. 2 parts of an.-

hydrous nickelous chloride are heated without a solvent at 230 to240 C. for two and one-half hours. The melt is cooled and extracted successively with acetone and water, and dried. The product obtained is a bronze-blue-crystalline powder which, upon grinding, turns to a darkgr'eenish blue. The compound appears to contain nickel in combined form.

a Example 2 1 0 parts of phthalonitrileand 3.4 parts of finely powdered nickel oxide are heated together with stirring at 280 C. for 4 hours. Thereaction mass is cooled, ground,- extracted with boiling acetone, and with boiling 7% hydrochloric acid, washed with water and dried. It is purified by 'crystallizing from technical chloronaphthalene, or by subliming or by dissolving in sulphuric acid and precipitating with water. The sublimation purification yields needles with an extremely bright red lustre.

Example 3 6.5 parts of phthalonitrile and 2 parts of cobaltous chloride are heated at a temperature of 230 to 240 C. for half an hour. The melt is cooled and extracted successively with acetone and Water. Upon drying, a bronze colored crystalline powder is obtained which turns, upon grinding, to a dark-greenish blue. It contains cobalt in chemical combination.

Example 4 10.2 parts of pthalonitrile and 2.6 parts of an-' hydrous cobaltous chloride are intimately mixed and heated to 200 C. with stirring. The coloring matter is formed at once, the temperature rises and hydrogen chloride is evolved. The reaction- Example 5 10 parts of phthalonitrile are boiled for 4 hours with 3 parts of cobalt (which has been etched immediately before use by Warming with dilute hydrochloric acid, washing and drying). The reaction mass is cooled, and the excess metal is removed by mechanical means. The residue is ground and extracted with boiling alcohol and dried.' The coloring matter is very soluble in boiling quinoline and technical chloronaphthalene. It can also be sublimed and then yields blue needles with a reddish-purple lustre. It dissolves in concentrated sulphuric acid with a green color and from the solution water precipitates the coloring matter without removing the combined nickel. It has the empirical f0rm111a'C32I-I1eN8CO.

Example 6 Example 7 A mixture of 16.25 parts of 4-chlorophthalonitrile, 3.25 parts of anhydrous nickelous chloride and 5 parts of technical chloronaphthalene is heated with stirring at about-230-240 C. for 4 hours. The reaction mass is cooled, ground and extracted successively with boiling xylene, hot alcohol and water. It is purified by dissolving in 10 times its weight of concentrated sulphuric acid, and pouring the solution into water, filtering,

washing and drying. It is greenish-blue in color and contains combined metal.

Example 8 v Example 9 A mixture of 4 parts of anhydrous nickelous chloride and 6 parts of 4,5-dichlorophthalonitrile is heated'at 240-250 C. with stirring for 4 hours. The reaction mass is cooled, extracted with boiling acetone, then With 7% hydrochloric acid, washed with water and dried. A greenish.

blue coloring matter: containing combined metal similar to that of Example '7 is obtained.

In a similar manner, coloring matter may be prepared from substituted phthalonitriles such as 3- or 4-chloro-phthalonitrile and 4.5-dichlorophthalonitrile and 3- or 4-nitro-phthalonitrile or methyl phthalonitriles.

It will be understood that the details of procedure given above, for instance as to solvent employed, temperature and duration of the reaction, method of extraction and purification, etc., may be interchanged between the various examples, and may be varied further within Wide limits, without departing from the spirit of this invention.

We claim:

1. The process of producing coloring matters of the phthalocyanine series which comprises subjecting an o-arylenedicyanide to the action of heat in the presence of a substancecapable of yielding a magnetic metal.

' 2. The process of producing coloring matters of the phthalocyanine series which comprises heating an o-arylene-dicyanide at a temperature between to 400 C. in the presence of a substance capable of yielding a metal of the group consisting of iron, nickel and cobalt.

3. The process of producing coloring matters of the phthalocyanine series which comprises heating an o-arylenedicyanide in a solvent which is liquid under the given conditions, in the presence of a member of the group consisting of iron, nickel, cobalt and their compounds which are capable of yielding the respective metals in chemical reactions;

4. The process of producing coloring matters of the phthalocyanine series which comprises heating phthalonitrile and nickelous chloride at a temperature of about 230 to about 240 C. and recovering the pigment thus produced.

5. The process of producing coloring matters of the phthalocyanine series which comprises heating phthalonitrile and cobaltous chloride at a temperature of about 230 to about 240 C. and recovering the pigment thus produced.

ISIDOR MORRIS I-IEILBRON. FRANCIS IRVING. REGINALD PATRICK LIN'STEAD. 

